DE2918883A1 - FLAME-RESISTANT PC ALLOYS WITH INCREASED STRESS-CORROSION RESISTANCE - Google Patents

Description

BAYER AKTIENGESELLSCHAFT 5090 Leverkusen, Bayerwerk

Central area PS / W

Patents, trademarks and licenses

1979

Flame-retardant PC alloys with increased resistance to stress cracking

The present invention relates to molding compositions consisting of

a) thermoplastic aromatic polycarbonates based on bis (hydroxyaryl) alkanes, cycloalkanes, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane or 4,4'-dihydroxydiphenyl sulfone,

b) an organic halogen compound, preferably an aromatic organic halogen compound and in particular a bromine and / or chlorine compound,

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c) an alkali or alkaline earth salt of an inorganic protic acid or an organic one Brönsted acid with at least one carbon atom, preferably an alkali salt, in particular

a Li, Na or K salt,

d) a substance that reduces the dripping tendency of polycarbonates, such as polytetrafluoroethylene, Polysiloxanes, glass fibers or carbon fibers,

which are characterized in that they

e) contain another thermoplastic which, after 6 days of storage in air at 80 ° C according to the test method described in "Kunststoffe" 65 (1975) 3, pages 155-157, has a limit strain £ _ma3C '

of at least 1.4 % , with as additional

Thermoplastic _s
for example
e 1) ABS polymers,

e 2) polyalkylene esters based on aromatic .PoIycarbonsäuren and aliphatic polyols,

e 3) aliphatic polyamides based on aliphatic polycarboxylic acids and aliphatic polyamines or based on aliphatic aminocarboxylic acids
e 4) polyphenylene oxides or
e 5) polyolefins
Can be used.

The improvement in the flame resistance of thermoplastic polycarbonates can be achieved in a known manner 30 through the addition or incorporation of halogen compounds, Salts of organic or inorganic

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Acids, such as alkali salts in particular, and optionally a substance that reduces the tendency of polycarbonates to drip off suppressed in the event of fire, as for example in DOS 21 48 589 (Le A 1? 970) and in the DOS 27 03 710 (Le A 17 759) is described.

The present invention relates to flame-retardant polymer alloys for use in the high-temperature range. The polymer alloys according to the invention are obtained by admixing suitable other thermoplastics to flame-retardant polycarbonate molding compositions, whereby flame-retardant polycarbonate alloys with an opposite pure polycarbonate with increased stress corrosion cracking resistance.

a) As the flame-retardant polycarbonate alloys according to the invention underlying thermoplastic aromatic polycarbonates are homopolycarbonates and / or copolycarbonates from bis (hydroxyaryl) alkanes and / or bis (hydroxyaryl) cycloalkanes and / or bis (4-hydroxyphenyl) ether and / or bis (4-hydroxyphenyl) sulfide and / or 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane and / or 4,4'-dihydroxydiphenyl sulfone Understood; Hydroxyaryl radicals in this connection are in particular hydroxyphenyl radicals, and very particularly 4-hydroxyphenyl radicals to understand, which can also carry substituents. Preferred alkanes are C ^ -Cc-alkylidenes and Cj-Cc-alkylenes, as cycloalkanes

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■ / -

are preferably Cr-C ^ Q-Cycloalkylidene- and To understand Cc-C ^ Q-Cycloalkylenes. According to the invention Suitable polycarbonates can be based on one or more of the following diphenols:

2,2-bis (4-hydroxyphenyl) propane 2,4-bis (4-hydroxyphenyl) -2-methylbutene 1,1-bis- (4-hydroxyphenyl) -cyclohexane ο ^, οΟ -bis- (4-hydroxyphenyl) -p-diisopropylbenzene 2,2-bis (3-methyl-4-hydroxyphenyl) propane 4,4'-dihydroxydiphenyl sulfide

2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) propane and 4,4'-dihydroxydiphenyl sulfone.

These and other suitable diphenols are described, for example, in U.S. Patent 3,038,365, in German 15 Offenlegungsschriften 1 570 703, 2 063 050 and in Monograph "H. Schnell, Chemistry and Physics of Polycarbonates, Intersience Publishers, New York, 1964" described.

Preferred diphenols e.g.

2,2-bis (4-hydroxyphenyl) propane 1,1-bis (4-hydroxyphenyl) cyclohexane * ΌΟ -Bis- (4-hydroxyphenyl) -p-diisopropylbenzene 4,4 · -dihydroxydiphenyl sulfide and 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane.

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Preferred aromatic polycarbonates are those containing one or more of the diphenols mentioned as preferred underlie. Copolycarbonates containing 2,2-bis (4-hydroxyphenyl) propane are particularly preferred and one of the other diphenols mentioned as preferred. Polycarbonates are also particularly preferred based solely on 2,2-bis (4-hydroxyphenyl) propane.

The aromatic polycarbonates can be produced by known processes, for example by the melt transesterification process from bisphenol and diphenyl carbonate and the two-phase interface process from bisphenols and phosgene as described in the literature cited above.

The aromatic polycarbonates may be prepared by the incorporation of small amounts, preferably amounts between 0.05 and 2.0 mol% (relative to diphenols employed) of ¹ trifunctional or more than trifunctional compounds, particularly those having three or more than three

20 phenolic hydroxyl groups, be branched.

Polycarbonates of this type are, for example, in German Offenlegungsschriften 1 570 533, 1 595 762, 2 116 974, 2,113,347 and 2,500,092, British Patent 1,079,821 and U.S. Patent 3,511,514.

Some of the useful compounds having three or more than three phenolic hydroxyl groups are, for example Phloroglucinol, 4,4-dimethyl-2,4,6-tri- (4-hydroxy-

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phenyl) -lieptan-2, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptane, 1,3j5-tri (4-hydroxyphenyl) -benzene, 1,1,1-tri - (4-hydroxyphenyl) -ethane, tri- (4-hydroxyphenyl) -phenyl methane, 2,2-bis ~ / 4,4-bis (4-hydroxyphenyl) -cyclohexyl / -propane, 2, 4-bis ~ (4-hydroxyphenyl-isopropyl) -phenyl-2,6-bis- (2-hydroxy-5'-methyl-benzyl) -4-methylphenol, 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl ) -propane and 1,4-bis- (4,4 "» dihydroxytriphenylmethyl) -benzene. Some of the other three-functional compounds are 2 ^ -Dxhydroxybenzoic acid, trimesic acid, cyanuric chloride, 35 3-bis (4-hydroxyphenyl) -2- oxo-2,3-dihydroindole and 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole.

The thermoplastic aromatic polycarbonates should generally have weight average molecular weights average of 10,000 to about 20O ₀ OOO, have preferably 20 ", 000 to 80,000, as determined by the method of light scattering.

In the case of polycarbonate blends, the high-2o molecular polycarbonates with JyL from 10,000 to 200,000 small proportions of low molecular weight polycarbonates, e.g. with an average degree of polymerization of 2 - 20, can be added.

The polycarbonate molding compositions of the invention the following examples are based on the aromatic poly

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carbonates are homopolymers of 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A), which by reaction of essentially equimolar amounts of bisphenol A and phosgene according to the two-phase interface process with sodium hydroxide, Triethylamine and p-tert-buty! Phenol under standard conditions have been manufactured.

The relative solution viscosities of the polycarbonates are 1.24 to 1.36, measured at % strength by weight solution in methylene chloride.

are 1.24 to 1.36, measured at 25 ° C in a 0.5

b) Organic halogen compounds for the purposes of the present invention are:

Aromatic polycarbonates based on 2,2-bis- (3,5-dibromo-4-hydroxyphenyl) propane and / or 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane with a degree of condensation of 2-20 (cf. DOS 2 243 226).

Other halogen compounds for the purposes of the present invention are those with polycarbonate or another component of the polycarbonate alloy according to the invention Can be mixed and that at the temperatures at which the polycarbonate is processed will not evaporate. Suitable organic halogen compounds are, for example, in DE-OS 18 02 184, US-PS 3,535,300 (No. 98.1), DE-OS 27 44 016, US-PS 4,110,299 and the Japanese laid-open publications JA-OS 75-64337 and JA-OS 75-119041.

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Suitable halogen compounds for the purposes of the invention are, for example:

Tetrahalophthalimide (cf. DOS 2 703 710) decabromodiphenyl ether
Pentabromophenoxyethane

Tribromophenoxyethane

Decabromodiphenyl carbonate

Decachloridiphenylcarbonat di-tribromophenyl tetrabromophthalate or Di-trichlorophenyl tetrabromophthalate Tetrabromoterephthalic acid di-tribromophenyl ester or Di-trichlorophenyl tetrabromoterephthalate Tetrachlorophthalic acid di-tribromophenyl ester or Di-trichlorophenyl tetrachlorophthalate Di-tribromophenyl tetrachloroterephthalate or Di-trichlorophenyl tetrachloroterephthalate.

Suitable halogen compounds for the purposes of the present invention are also oligomeric or polymeric bromine and / or chlorine-containing compounds such as oligo- or polybromostyrenes or polychlorostyrenes (cf. DOS 26 45 415).

Suitable amounts of halogen-containing compounds for the purposes of the present invention are 0.01 to 5% by weight , based in each case on the total weight of the flame-retardant polycarbonate alloy.

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to

By condensing in suitable amounts of halogenated Bisphenols, such as, for example, tetrabromo- or tetrachlorobisphenol A, during the production of those according to the invention The aromatic polycarbonates a) on which molding compositions are based can likewise be incorporated the necessary halogen content in the polycarbonate alloys according to the invention.

c) Suitable alkali and / or alkaline earth salts for the purposes of the invention are, for example, those of inorganic ones Protonic acids. Inorganic protic acids in the context of the invention are Brönsted acids, which can form alkali or alkaline earth salts (for the expression "Brönsted acids" see Fieser & Fieser "Organic Chemistry", 1965, p. 595, interscience publishers N.Y., USA), such as sulfuric acid, Hydrofluoric acid, hydrochloric acid, hydrobromic acid, meta-, ortho- or pyro-phosphoric acid and protic acids of complex fluorometallic compounds. More complex than such alkali or alkaline earth salts Fluorometallic compounds can be used, for example:

Hexafluoroaluminate Hexafluorotianate Hexafluoroantimonate Hexafluorosilicates 25 Hexafluorotungstate Hexafluorozirconate Hexafluorophosphate Tetrafluoroborate.

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Suitable alkali or alkaline earth salts of organic acids are those of organic acids for the purposes of the invention Brönsted acids with at least one carbon atom that form alkali or alkaline earth salts can.

Such optionally substituted organic acids can be OH- or NH-acidic compounds, such as, for example, carboxylic acids, sulfonic acids, phosphonic acids, thiophosphonic acids, NH-acidic sulfonamides or sulfonimides, mono- or polyfunctional phenols or alcohols. You must have at least one carbon atom have and can preferably contain between 2 and 30 carbon atoms.

Suitable alkali or alkaline earth salts of organic Brönsted acids are also salts of the following Substance classes:

Phosphoric acid ester salts or phosphoric acid thioester salts of the general structures (I) and (II)

(RO) ₀ P-Ol-Me

'2

Il Jn

(RO) - P.

^Me m

(I) Y = 0, S (II) Y = 0, S

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with Me = alkali and η = 1 and m = 2; Me = alkaline earth

with η = 2 and m = 1
R = C ₁ - C ₂₀ alkyl, cycloalkyl, C ₂ - C ₂₀ alkenyl, cycloalkenyl, Cg - C ₁₈ aryl, where the aryl radical is optionally replaced by 1-4 halo + ^ e such as F, Cl or Br, by CN-, CF, - or C _{1 -C 18} alkyl or cycloalkyl or C _{2 -C 18} alkenyl or cycloalkenyl groups can be substituted.

Suitable alkali or alkaline earth salts for the purposes of the invention can also be those of the general structure (III) be:

(1-4)

(III) Y = 0, S.

with Me = alkali and η = 1 Me = alkaline earth and η = 2 X = F, Cl, Br, CN, CF,

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Furthermore, alkali or alkaline earth salts of the general structure (IV) can be used:

Me (IV) Y = 0, S.

with Me = alkali and η = 1; Me = alkaline earth and η = 2 R = R of structure (i) or (II).

Suitable alkali salts are the Li, Na and K salts. Suitable alkaline earth salts are the calcium salts. The salts are also those described in DOS 27 03 710 Manner in an amount of 0.02 to 1 wt .-%, preferably 0.04 to 0.5 wt .-%, based on the Total weight of the polycarbonate alloy added.

Further suitable alkali and / or alkaline earth salts within the meaning of the invention are for example in the DOS 24 60 935, 24 60 944, 24 60 945, 24 60 946, 24 61 145, 25 35 261, 25 35 262, 25 35 263, 26 31 756, 26 43 256, 26 44 114, 26 45 415, 26 46 120, 26 47 271,

26 48 131, 26 53 327, 26 48 128, 27 44 015, 27 44 016,

27 44 017, 27 44 018, 27 45 592, 27 46 906.

Preferred salts are the alkali salts and again below the Li, Na and K salts.

The alkali metal salts and alkaline earth metal salts suitable according to c) should preferably have a pH value between 5 and 9, in particular between 6.5 and 7.5, measured on 1% by weight solutions or suspensions of the salts in water at 20 ^° C.

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d) Suitable substances that reduce or completely suppress the dripping of polycarbonates, especially in the event of fire, are in the interest
of the invention substances such as polytetrafluoroethylene

(cf. DOS 25 35 262), polysiloxanes (cf. DOS 25 35 261) and glass fibers (cf. DOS 25 35 263 and DOS 21 48 598). These materials are 0.01 to 3 wt .-%, based on the total weight of the polycarbonate alloy, in contain the polycarbonate alloys according to the invention.

e) Suitable ABS polymers for the purposes of the invention are prepared by polymerizing monomers, preferably styrene and acrylonitrile, in the presence of a diene rubber. In these products, a monomer mixture of 95-50 % by weight of styrene and 5 to 50 % by weight of acrylonitrile is polymerized in the presence of a rubber. The graft polymer can consist of 80-10 parts by weight of rubber and 20-90 parts by weight of copolymer which is at least partially chemically bonded ("grafted") to the rubber.

Diene rubbers are in particular polybutadiene, butadiene / styrene copolymers with up to 30 wt .- # Polymerized styrene, copolymers of butadiene and acrylonitrile with up to 20% by weight

a lower alkyl ester of acrylic or meth-

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acrylic acid (ζ "Β. methacrylate, ethyl acrylate, methyl methacrylate and ethyl methacrylate). Ethylene / propylene / diene polymers, so-called EPDM systems, are also suitable. In principle, all elasticizing components can be used as "diene rubbers", as long as they show rubber-elastic behavior and the required resistance to stress corrosion cracking. The graft polymers can be prepared in a known manner by free-radical polymerization of styrene and acrylonitrile in the presence of the rubber in substance, emulsion

(according to DT-AS 1 247 665 and 1 269 360), suspension and combined processes such as bulk / suspension polymerization or solution / Pällungspolymerisierung obtained will.

To explain the subject matter of the invention, two ABS polymers described in Examples 6 and 7 were used Products used. These are ABS polymers made from a graft of styrene and acrylic = nitrile to a coarse polybutadiene according to the

20 graft polymer produced by emulsion polymerization (the mean particle diameter of the polybutadiene graft base in latex form is between 0.3 and 0.4 μm), the one with a styrene-acrylonitrile copolymer by common precipitation of the

corresponding latices was mixed.

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Polyalkylene esters suitable according to the invention based on aromatic polycarboxylic acids, in particular dicarboxylic acids, in particular based on terephthalic acid and / or isophthalic acid, and on aliphatic polyols, in particular diols, e.g. ethylene glycol, propanediol-1,3, butanediol-1,4, hexanediol-1,6 and 1 , 4-Bishydroxymethylcyclohexane have mean weight average molecular weights M ^ of 10,000 to 80,000. (Measured according to the light scattering method in phenol / 1,2-dichlorobenzene 50% by weight: 50% by weight). Polyalkylene esters such as polyalkylene terephthalates can be obtained by known processes, for example from dialkyl terephthalate and the corresponding diol, by transesterification (see, for example, US Patents 2,647,885, 2,643,989, 2,534,028, 2,578,660, 2,742,494, 2,901,466). For example, one starts from a lower alkyl ester of terephthalic acid, preferably the di-methyl ester, and esterifies this with an excess of diol in the presence of suitable catalysts to give the bishydroxyalkyl ester of terephthalic acid. The temperature is increased from 140.degree. C. to 210.degree.-220.degree. The alcohol released is distilled off. Condensation is then carried out at temperatures of 210 ° - 280 ⁰ C, the pressure is gradually reduced to less than 1 Torr lowered, the excess diol is distilled off.

A polybutylene terephthalate (Examples 8 and 9) was used as the polyester. This is made from 1,4-butanediol and dimethyl terephthalate according to known methods.

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"Ζ"

Suitable aliphatic polyamides based on aliphatic polycarboxylic acids and aliphatic polyamines in the context of the invention are in particular by polycondensation of aliphatic diamines, 5 aliphatic dicarboxylic acids and aminocarboxylic acids

or amide-forming derivatives of these classes of compounds, such as dicarboxylic acid halides, esters, nitriles or amides or lactams, in a known manner and under usual conditions. Polyamides used with preference are those based on hexamethylenediamine and adipic acid or sebacic acid and based on ε-aminocaproic acid or ε-caprolactam. According to the invention Polyamides to be used have mean weight average molecular weights J ^ from 10,000 to 100,000. (Measured using the light scattering method in 36 # sulfuric acid). When polyamides were Polyamide-6 (example 10) made from ε-caprolactam, and polyamide-6,6 (Example 11) made from hexamethylenediamine and adipic acid were used.

20 Suitable polyphenylene oxides are in particular poly

(2,6-dialkyl-1,4-phenylene oxides) and among them very particularly the poly (2,6-di (C ₁ -C 4 -alkyl) -1,4-phenylene oxides) such as, for example, poly (2,6 dimethyl-1,4-phenylene oxide You can by known processes

25 oxidizing condensation of 2,6-dialkylphenols with

Oxygen in the presence of catalyst combinations of copper salts, such as copper (i) chloride and tertiary amines such as pyridine.

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-Vf-

(See, for example, DT-OS 2,126,434 and U.S. patents 3 306 875, 3 221 080). The poly (2,6-dialkyl-1,4-phenylene oxides) according to the invention have mean weight average molecular weights of 2,000 to 100,000, preferably from 20,000 to 60,000 (measured by the light scattering method in chloroform).

Suitable polyolefins for the purposes of the invention are polymers of aliphatic unsaturated hydrocarbons, such as, for example, ethylene, propylene, butylene or isobutylene, which by conventional methods, for example by radical or Ziegler-Natta polymerization can be produced can and mean weight average molecular weights JL from 25,000 to 500,000. (Measured according to the light scattering method in decalin).

15 It is both high pressure polyolefin and low pressure polyolefin suitable. The unsaturated hydrocarbons can be mixed with other vinyl monomers be copolymerized in a known manner.

A high-pressure polyethylene (Examples 4 and 5) was used to explain the subject matter of the invention in more detail.

The polycarbonate molding compositions according to the invention contain the additives b), c), d) and e) in the following amounts based in each case on the total weight of the polycarbonate alloy:

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in quantities - each - 5 Wt .-%, Il from 0.01 to 2 Wt% the addition b) If 0.1 to 1 Wt% preferably II 0.2 to 1 Weight -96 ' in particular Il 0.02 to 0 , 5% by weight the addition c) Il 0.04 to 0 , 2% by weight, 5. preferably in quantities 0.05 to 3 Wt% in particular from 0.01 to 1 Wt% the addition d) "0.03 to 0 , 7% by weight, preferably "0.05 to 10 Wt .-%, in particular " 1 to 10 Wt .-%, 0 the addition e) »3 to 10 Weight-96. preferably »5 to in particular

The composition of the polycarbonate alloys according to the invention is chosen so that the additives b, c, d and 15e add up to 100% by weight with the underlying polycarbonates a), which means that the polycarbonate component a) in amounts between 81 and 98.96 wt .-% _s based on the total weight of the five-component mixture, may be present.

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By adding component e), the inventive Polycarbonate molding compositions whose resistance to stress corrosion cracking can be improved.

The molding compositions according to the invention can be produced in any desired manner. You can do it in a single stage Mixing process by simultaneously mixing together all components according to the invention or by successive mixing of the individual components, for example in single or twin-screw extruders getting produced. '

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Thus, the molding compositions according to the invention can be prepared by adding to a mixture of component a) and one of the components t>) to e) adds the remaining components simultaneously or successively.

Furthermore, the molding compositions according to the invention can be prepared by adding components b) to e) a portion of component a) is mixed and this mixture is combined with the remainder of component a).

In addition, the molding compositions according to the invention can be produced in such a way that a mixture is obtained of component a) with two of components b) to e) the remaining components simultaneously or successively admits.

The components can be mixed:

^C 1) by simultaneous or successive mixing of the individual components a) to e) and extruding them together,

2) by dissolving the thermoplastics a) and e) in one

Solvent suitable for the respective thermoplastic and subsequent evaporation of the liquid Phases and subsequent simultaneous or successive addition of the remaining components b), c) and d) during extrusion.

3) by producing a concentrate from components b), c) and d) with a subset of components a)

25 and subsequent combination with the remaining amount a) with simultaneous or successive addition of the component e) during extrusion,

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4) by mixing two concentrates (I) and (II), where

(I) consists of mixtures of component e) with some of components b), c) and / or d)

5 and where

(II) consists of mixtures of a subset of component a) with the respective complementary part of components b), c) and / or d) and

subsequent dilution of the two concentrates (i) and (II) by the required residual amount of polycarbonate according to component a) during the extrusion.

The molding compositions according to the invention can be used during or after their production according to the customary thermoplastic Processing methods such as extrusion into molded parts and films with improved flame retardancy and increased temperature resistance. In addition, they can be processed into cast films will.

The flame-retardant polycarbonate alloys according to the invention other materials such as antistatic agents, pigments, mold release agents, thermal stabilizers, ultraviolet light stabilizers and reinforcing fillers are mixed.

The added thermoplastic components e) can also

25 if stabilized in the usual way.

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The molding compositions according to the invention can be used wherever flame-retardant polycarbonates have been successfully used up to now (e.g. in Electrical and mechanical engineering sectors) and where there are also increased demands on the Stress corrosion cracking resistance are made, for example in the automotive industry, where a Resistance to petrol, oil and cleaning agents is required.

The inventive methods obtained in the following examples by the processes described above flame-retardant polycarbonate alloys were extruded at 280 ° C. and comminuted into granules.

A measure of the stress corrosion cracking resistance is the drop in mechanical properties, e.g.

Elongation at break as a function of the outer fiber elongation, which is generated by a defined bending of the test specimen. With the help of a series of deformations of different outer fiber elongations, the limit elongation ^ T _3n Jo _{x is} sought, which does not lead to damage under the other constant conditions. The limit elongation depends on the specimen condition, the environmental influence, the temperature and the time.

The test is carried out as follows:

The polymer mixtures according to the invention are made by the known methods - injection molding - shoulder

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Rods of 2 mm thickness were produced. These were clamped with two clamps in the shape of a circular arc onto the surfaces of templates made of chemical-resistant material, which were curved with the radius r. This results in an edge fiber strain of the amount £ _b ~ d (2r + d) · 100 f% _7 (d = sample thickness) in the tensile zone of the test rods. By using different template radii of curvature, the edge fiber strains can be varied in small steps in the area of the limit strain to be expected.

The clamped test specimens are ^{treated in air at 80 °} C. for 144 hours (6 days). The elongation at break is then measured in accordance with DIN 53 455.

The examined value of the elongation at break is plotted as a function of the applied outer fiber elongation £ _b . In the event of material damage, the property curve runs in steps. The outer fiber strain that can be assigned to the steep drop is the sought-after limit strain £ _bmax .

This test method is described in the journal published by Carl Hanser-Verlag, Munich "Kunststoffe» 65 (1975), 3, pages 155-157.

The flame resistance test was carried out according to the test method according to Underwriters Laboratories, Inc. Bulletin 94, Combustion test to classify materials

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(called UL-94 for short). Here, the flame-retardant polycarbonate alloys of the invention by injection molding at 300 are out of granules - mm 310 ⁰ C the test bars in two specimen thicknesses of 1.6 and 3.2 mm produced 5 and tested according to UL-94.

According to this residual procedure, the materials tested in this way were rated either with UL-94 V-O, UL-94 V-I and UL-94 V-II classified based on the results obtained on the 10 samples. The criteria for each of these V-classifications according to UL-94 briefly as follows:

UL-94 V-O The average flame and / or glow after removal of the pilot flame should Do not exceed 5 seconds and none of the samples should drip off any particles ignite absorbent cotton.

UL-94 V-I The average flame and / or glow after removal of the pilot flame should Do not exceed 25 seconds and none of the samples should drip off particles that ignite absorbent cotton.

UL-94 V-II The average flaming and / or

Glowing after removal of the pilot flame should not exceed 25 seconds and the Samples drop flaming particles which ignite absorbent cotton.

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2818883

if

25 -

Furthermore, a test stick that burned for more than 25 seconds after removing the pilot flame did not persist UL-94 classified, but has been classified as the same according to the standard conditions of the present invention "burns" called. The UL-94 regulation also requires that all test sticks in an experiment have the must meet the respective V-rating, otherwise the 10 test sticks receive the rating of the worst Single rod. For example, if 1 stick is rated UL-94 V-II and the other 9 test sticks are rated with UL-94 V-O, then all 10 bars receive the rating UL-94 V-II.

The results are compiled in the examples in Table 1 below. That in the examples aromatic polycarbonate used is a homopolycarbonate based on bisphenol A with a Weight average molecular weight of JS ^ = 30,000.

Examples 1, 2 and 3 serve as comparative examples :

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Tabel

CoBei- flame retardant additives wt .-% thermoplastic additives wt .-% UL-94 C

^ play b, c, dr, 6 3 _± 2 <~

ΟΛ
VO-

ΐηώ mm

Trisodium hexaf luor oaliiminate 0.25

N-methyl tetrachlorophthalimide 0.50 Hostafion TP 2026Ό 0.10

VO VO 1 »4

Potassium hexafluorotitanate 0.25 N-methyltetrachlorophthalimide 0.25 Hostafion TF 23 ¹ ^

VO VO 1.4

Potassium hexafluorosilicate 0.25 N-phenyl tetrachlorophthalimide 0.50 Hostafion TF 2026 0.10

VO VO 1.4

Potassium hexafluorotitanate 0.25 polyethylene N-methyl tetrachlorophthalimide 0.25 Hostafion TF 2053 0.10

5.0 VO VO 1.6

OO OO OO

At- Flame retardant.e additives
^ play b, c, d

Continued table

Wt -.% Thermoplastic additives

Wt% UL-94

1.6 3.2 mm mm

_ffiax

Potassium hexafluorosilicate 0.25 N-phenyl tetrachlorophthalimide 0.50 Hostafion TF 2053 0.10

Polyethylene 7.5 VO VO 1.8

Triatrium hexafluoroaluminate 0.26 N-phenyl tetrachlorophthalimide 0.50 Hostafion TF 2026 0.10

ABS polymer

2.5 VO VO

1.7

~ * 7 Potassium hexafluorosilicate 0.25 β »N-phenyltetrachlorophthalimide 0.50 ** »Hostaflon TF 2026

ABS polymer

7.5 VO VO

1.9

? fe

Trinatrium hexafluoroaluminate 0.25 Polyhutylene terephtha-N-phenyltetrachlorophthalimide 0.50 lat ¹ V Hostafion TF 2026 0.10

2.5 VO VO 1.6

CO OO CO

Continued table

Examples Flaminhemmende additives wt .- $ thermoplastic additives wt -.% UL-94 C.

ίο games b, c, d 1.6 3.2 ^{cb ma} *

mm mm

Potassium hexafluorotitanate 0.25 polybutylene-N-methyltetrachlorophthalimide 0.50 terephthalate Hostaflon TF 2026 0.10

7.5

VO VO

1.9

Potassium hexafluorotitanate 0.25 polyamide-6

N-methyl tetrachlorophthalimide 0.50 Hostafion TF 2026 0.10

5.0

VO VO

1.7

Potassium Hessafluorosilicate 0.25 Polyamide 6.6

N-phenyl tetrachlorophthalimide 0.50 Hostafion TF 2053 0.10

7.5

VO VO

1.8

Polytetrafluoroethylene: Manufacturer: Hoechst AG, made from tetrafluoroethylene

Continued Table 1
2) Polyethylene: Manufacturer: Chem. Werke Hüls, Mw 52,000, made from ethylene

ABS graft polymer: Manufacturer: Bayer AG, produced from 60% by weight of a polybutadiene / SAN graft copolymer and 40 percent by weight! of a SAN copolymer.

Polybutylene terephthalate: Manufacturer: Bayer AG, Mw "6O 000, made from 1,4-butanediol and dimethyl terephthalate

CO 00 OO

Continued Table 1

5) polyamide-6; Manufacturer: Bayer AG, relative solution viscosity

(Measured in 1% meta-cresol solutions)
• ^ rel. = 2.93
made from ^ -Caprolactam

O 6) Polyamide-6,6 Manufacturer: BASF, relative solution viscosity

^ t (measured in 1% meta-cresol solutions) ι

^ ^ 7rel. = 4.06

_ »Made from hexamethylenediamine and

° * adipic acid

OD 00 OD

Claims (10)

Patent claims 1) Molding compounds, consisting of a) thermoplastic aromatic polycarbonates based on bis (hydroxyaryl) alkanes, Bis (hydroyaryl) cycloalkanes, 4,4'-dihydroxy diphenyl ether, 4,4'-dihydroxy diphenyl sulfide, 2,2-bis (3,5-dimethyl-4-hydroxy- phenyl) propane or "Ό 4,4'-dihydroxydiphenyl sulfone b) an organic halogen compound, c) an alkali or alkaline earth salt of an inorganic protic acid and / or an organic Erönsted acid with at least one carbon atom, d) a substance that reduces the dripping tendency of poly- carbonate reduced,
characterized in that they e) contain a further thermoplastic which has a limit elongation P_ ^ of at least 1.4 % . 2) Molding compositions according to claim 1, characterized in that they contain the polycarbonate component a) in amounts of 81 to 98.96% by weight, based on the sum of the components a + b + c + d + e. 030047/0187 - ■ 32- 3) Molding compositions according to claim 1, characterized in that they contain the organic halogen compound b) in amounts of 0.01 to 5% by weight, based on the sum of the components a + b + c + d + e. 4) molding compositions according to claim 1, characterized in that that they are the alkali and / or alkaline earth salts c) an inorganic acid or an organic Brönsted acid with at least one carbon atom in amounts of 0.02 to 1 wt .-%, based on the sum of the Components a + b + c + d + e included. 5) molding compositions according to claim 1, characterized in that that they the dripping tendency of the polycarbonates reducing additive d) such as polytetrafluoroethylene, Polysiloxanes or glass fibers in amounts from 0.01 to 15 3% by weight, based on the sum of the components a + b + c + d + e. 6) molding compositions according to claim 1, characterized in that that they are further thermoplastics e) ABS polymers, polyalkylene esters, aliphatic polyamides, poly . 20 phenylene oxides or polyolefins in amounts of 1.0 to 10 wt .-%, based on the sum of the components a + b + c + d + e. 7) Process for the preparation of molding compositions according to Claims 1 to 6, characterized in that one 25 either Le A 19 569 030047/0187 1) to a mixture of component a) and one of components b) to e) the remaining Adding components simultaneously or successively, or 2) the components b) to e) mixed with a portion of the components a) and this mixture combined with the remaining amount of component a), or 3) by adding to a mixture of component a) with two of the components b) to e) the remaining components simultaneously or successively admits. 8) Use of the molding compositions according to Claims 1 to 6, optionally after the addition of antistatic Agents, pigments, mold release agents, thermal stabilizers, ultraviolet light stabilizers and reinforcing fillers, for the production of molded parts and films. 9) Use of the molding compositions according to claims 1 to for the production of molded parts and foils by injection molding or extrusion. 10) Use of molding compositions according to Claims 1 and 8 for the production of cast films. 030047/0187